Treatment of keratinous fibres and fabrics with polythiols

ABSTRACT

A PROCESS FOR MODIFYING KERATINOUS MATERIALS BY USING A POLYTHIOL ESTER OF THE FORMULA   (HO-(R&#39;&#39;-O)A)QY-R(-((CO)X-(O-R1)AY-O-(CO)Y-R2-SH)P)-   (CO2H)QX   WHEREIN R REPRESENTS A HYDROCARBON RADICAL, CONTAINING A CHAIN OR AT LEAST 3 AND AT MOST 60 CARBON ATOMS, R1 REPRESENTS AN ALKYLENE GROUP CONTAINING AT LEAST 2 AND AT MOST 6 CARBON ATOMS, R2 REPRESENTS A HYDROCARBON RADICAL, A, X, AND Y IN EACH OF THE P CHAINS ARE INDIVIDUALLY CHOSEN FROM THE GROUP COMPRISING ZERO AND 1, WITH THE PROVISO THAT X AND Y ARE UNEQUAL, P IS AN INTEGER OF AT LEAST 3 AND AT MOST 6, Q IS CHOSEN FROM THE GROUP COMPRISING ZERO AND POSITIVE INTEGERS OF AT LEAST 1 AND AT MOST 3, (P+Q) IS AT MOST 6, OPTIONALLY IN COMBINATION WITH OTHER POLYMERIC POLYMEROPTIONALLY IN COMBINATION WITH OTHER POLYMERIC POLYMERCAPTANES, AMINOPLASTS, EPOXY RESINS, ACRYLIC RESINS, ACRYLAMIDE OR POLYISOCYANATES. THE POLYMERS CURE ON THE FIBRE. THE KERATINOUS MATERIALS ARE RENDERED RESISTANT TO SHRINKAGE AND DURABLE PRESS CHARACTERISTICS ARE IMPARTED TO THEM. THE TREATED MATERIAL RETAIN THEIR DIMENSION AND SHAPE WHEN WASHED IN MACHINES AND HAVE GOOD RECOVERY FROM WRINKLING.

United States Patent Office 3,706,527 Patented Dec. 19, 1972 3,706,527TREATMENT OF KERATINOUS FIBRES AND FABRICS WITH POLYTHIOLS BryanDobinson, Duxford, and Kenneth Winterbottom, Whittlesford, England,assignors to Ciba-Geigy AG No Drawing. Filed Aug. 25, 1970, Ser. No.66,903 Claims priority, application Great Britain, Sept. 2, 1969,

43,478/69 Int. Cl. D06m 3/06, 13/20, 13/26 US. Cl. 8127.5 19 ClaimsABSTRACT OF THE DISCLOSURE A process for modifying keratinous materialsby using a polythiol ester of the formula -oo OH] L q:

R represents a hydrocarbon radical, containing a chain of at least 3 andat most 60 carbon atoms,

R represents an alkylene group containing at least 2 and at most 6carbon atoms.

R represents a hydrocarbon radical,

a, x, and y in each of the p chains are individually chosen from thegroup comprising zero and l, with the proviso that x and y are unequal,

p is an integer of at least 3 and at most 6,

q is chosen from the group comprising zero and positive integers of atleast 1 and at most 3,

(p-l-q) is at most 6,

optionally in combination with other polymeric polymercaptanes,aminoplasts, epoxy resins, acrylic resins, acrylamide orpolyisocyanates. The polymers cure on the fibre. The keratinousmaterials are rendered resistant to shrinkage and durable presscharacteristics are imparted to them. The treated material retain theirdimension and shape when washed in machines and have good recovery fromwrinkling.

wherein The present invention relates to a process for modifyingkeratinous material, and, in particular, to a process for rendering thematerial resistant to shrinkage and to a process for imparting durablepress characteristics to the material.

A number of shrink-resist processes for keratinous material are known,some of which comprise the application of a resin to the material whichmay be in fabric or fibre form. Shrink-resist processes stabilize thedimensions of keratinous materials against shrinkage due to felting.

Durable press processes for keratinous material are also known and manyof them employ resins the same or similar to those used in shrink-resistprocesses. In some durable press processes the desired shape is impartedto the keratinous material before the resin is cured and then curing isallowed to take place whilst the material is maintained in the desiredshape, e.g. in form of creases or pleats. In others the resin is appliedafter the desired shape is imparted to the material. Durable pressprocesses stabilize the shape and surface smoothness of the materialagainst deformation in the presence of aqueous solutions. The desiredshape may be imparted to the material before or after resin treatment bywell known methods involving the use of setting agents such as water,reducing agents, and bases.

A desirable, though not essential, feature of shrinkresist and durablepress processes is that the keratinous material so treated should bewashable in domestic washing machines. To be machine-washable the finishon the treated material should withstand vigorous agitation in warm orhot water containing detergents, and this requirement sets a sever testfor the durable press and shrink-resist treatments.

We have now found that certain thiol-terminated esters can be used indurable press and shrink-resist processes successfully. These esterscure, i.e. undergo reaction, on the keratinous fibre and we have furtherfound that the rate of curing may be largely controlled by selection ofthe appropriate catalyst.

Accordingly, the present invention provides a process for modifyingkeratinous material which comprises (1) Treating the material with apolythiol ester of the formula wherein R represents a radical,containing at least 3 carbon atoms, preferably an aliphatic oraraliphatic hydrocarbon radical of at most 60 carbon atoms, other than aradical of a polyhydric alcohol having at least two oxyalkylene chainsattached thereto with the indicated radicals attached to the saidoxyalkylene chains,

R represents an alkylene group containing at least 2 and at most 6carbon atoms,

R represents a hydrocarbon radical,

a, x, and y in each of the p chains individually represent zero or 1,with the proviso that x and y are unequal,

p is an integer of at least 3 and at most 6-,

q is zero or a positive integer of at most 3,

(p+q) is at most 6, and

(2) Curing the polythiol ester on the material.

This invention also provides keratinous fibrous materials, in the formof fabrics if desired, bearing thereon a polythiol as aforesaid in thecured or still curable state.

The treatment according to the invention, whether to achieveshrink-resist or durable press effects, provides fibres or garmentswhich will withstand washing in ma chines and still retain theiroriginal dimension and shape. The treated material also has goodrecovery from wrinkling, which is an important attribute in fabricsemployed in trousers where there is a strong tendency to wrinkles in theareas of the knee and back of the knee. Of course, wrinkle-resistance isan important advantage in many garments.

The polythiols used in the process according to the invention, as wellas inhibiting or preventing felting shrinkage, also inhibit or preventrelaxation shrinkage, which is an important problem associated with bothknitted and Woven goods.

The term keratinous material as used throughout this specificationincludes all forms of keratinous fibres or fabrics and garments madetherefrom, e.g. fleeces, tops, card sliver, noils, yarns, threads, pilefabrics, non-woven fabrics, woven fabrics, and knitted goods. Thetreatment may be applied to fabrics or made-up garments but it may bedesirable in some circumstances to shrink-resist fibres, e.g. in theform of tops. Indeed, treatment of keratinous material as loose wool,sliver, slubbing, tops, and yarns in the form of hanks or packages is aparticularly suitable embodiment of the invention: in some casestreatment leaves a slightly harsh film on the fibre, but this film islargely removed on subsequent mechanical handling of the fibre, e.g. inweaving. The material to be treated can consist either wholly ofkeratinous fibres or of blends of these fibres with synthetic fibrousand filamentary material such as polyamides, polyesters, andpoly(acrylonitrile) and with cellulosic, including regeneratedcelluosic, material. In general, however, the material should contain atleast 30% by weight of keratinous fibres and better results are obtainedwith 100% keratinous fibre-containing material.

The keratinous material may be virgin or reclaimed: preferably, thoughnot necessarily, it is sheeps wool. It may also be derived from alpaca,cashmere, mohair, vicuna, guanaco, camel hair, and llama, or blends ofthese materials with sheeps wool.

Preferred polythiols are those of formula FOR] [1.

in which group.

One perferred class of such polythiol esters are those of formula OE]]/E q OCOR*-SH] L p m and further preferred are those which also conformto Formula IV o-o OR=SH] D where R, R p, and q have the meaningspreviously assigned and R denotes an aliphatic hydrocarbon radicalhaving at least 3 and at most 6 carbon atoms.

These polythiols are, in general known substances, and are readilyprepared by partial or complete esterification of a polyol [R] [OH] (1,)with a mercaptocarboxylic acid HOOC--R SH. The mercaptocarboxylic acidis preferably thioglycollic acid, 2-mercaptopropionic acid,3-mercaptopropionic acid, or mixtures thereof, although othermercapto-acids such as mercaptoundecylic acid, mercaptostearic acid, ando-mercaptobenzoic acid may also be used.

Polyols suitable for use as starting materials include glycerol,1,1,l-trimethylolethane, 1,1,1-trimethylolpropane, hexane-1,2,5-triol,hexane-1,2,6-triol, pentaerythritol, dipentaerythritol, mannitol,sorbitol, polyvinyl alcohol, styrene-allyl alcohol copolymers, partiallyhydrolysed polyvinyl esters or acetals, and hydroxyalkyl acrylate,methacrylate, and itaconate polymers and copolymers.

Most preferred are the polythiol esters of Formula IV where q is zero.

Another preferred class of polythiol esters are those of formula oo-o-n-sn t 1 Eooon] in which R and b have the meanings previously assigned,and R represents an alkylene group, such as one of formula C H where nis an integer which is at least 2 and may be as high as 9 or even 12,and is especially --CH CH or -CH CH(CH and u is zero or 1.

Further preferred are polythiols which are of the formula Polycarboxylicacids which can be used as starting materials include citric acid,tricarballylic acid, mellitic acid, trimellitic acid, pyromellitic acid,trimerised linoleic acid and polymers or copolymers of monoethylenicallyunsaturated acids and anhydrides such as acrylic acid, methacrylic acidand maleic anhydride.

The polythiols may be used alone or in conjunction with I aminoplasts,polymeric and non-polymeric polymercaptans, epoxy resins, (i.e.substances containing on average more than one 1,2-epoxide group permolecule), acrylic resins, including polymers and copolymers of acrylateesters, e.g. ethyl, n-butyl and Z-hydroxyethyl acrylates, andacrylamide, or polyisocyanates, including prepolymers of, for example, apoly(oxyalkylene) glycol and an aromatic diisocyanate or of apoly(oxalkylene) triol and an aliphatic diisocyanate.

Particuar useful polymeric polymercaptans for use with the polythiolesters are those esters or ethers 'which have at least two mercaptangroups per molecule and which contain (a) A radical of a polyhydricalcohol (b) Bound to this radical, at least two poly(oxyalkylene)chains,

(0) Bound through oxygen atoms to carbon atoms in the saidpoly(oxyalkylene) chains, at least two residues selected from the groupcomprising an acyl residue of a thiol-containing aliphatic carboxylicacid or a residue, after removal of a hydroxyl group, of athiol-containing aliphatic alcohol,

The said ester or ether having a molecular weight of at least 400 and atmost 10,000.

Examples of such said esters and ethers are those of the formula o-aiklene -on] 1 l. t

[ O-a1kylene OCHzCHCHzSH] H IX wherein R represents an aliphatic radicalcontaining at least 2 carbon atoms,

each alkylene group contains a chain of at least 2 and at most 6 carbonatoms between the indicated consecutive oxygen atoms,

.9 denotes an integer, which may have different values in each chain,

v denotes an integer of at least 2 and at most 6,

t denotes zero or a positive integer such that (t-i-v) is at most 6, and

R has the meanings previously assigned, especially such esters andethers having a molecular weight of from 1,000 to 5,000.

The aforesaid esters and ethers are commercially available.

Other polymeric polymercaptans which may be used with the polythiolesters of this invention include homopolymers or copolymers of butadieneor methylbutadiene having SH groups directly attached to carbon atoms ofthe polymer, such as those containing structures of formula in which band d are each a positive integer such that the polymer has an averagemolecular weight of at least 1,000 and at most 10,000,

is zero or a positive integer,

X represents hydrogen or methyl, and

Y represents CN, COOH, --CONH COOZ, C H or OCOZ, where Z is an alkylgroup of from 1 to 8 carbon atoms.

Thiol-terminated polybutadienes of this type are also commerciallyavailable.

There may also be used nonpolymeric polymercaptans such as thebis(thioglycollates) and bis(3-mercaptopropionates) of ethylene glycoland propylene glycol.

Many of the polythiol esters used in the process of this invention areinsoluble in water but can be applied as aqueous dispersions oremulsions. Preferably the poly thiols are applied to fabrics andgarments from organic solvents, for example alcohols, lower ketones suchas ethyl methyl ketone, benzene, and halogenated hydrocarbon solvents,especially chlorinated and/ or fluorinated hydrocarbons containing notmore than three carbon atoms such as the dry cleaning solvents, carbontetrachloride, trichloroethylene, and perchloroethylene.

The amount of polythiol used depends on the effect desired. For mostpurposes 0.5 to 15% by weight based on the material treated ispreferred. Stabilization of knitted fabrics usually requires from 1 toby weight of the resin. A high level of shrink-resistance,crease-setting and substantial resistance to wrinkling can be achievedon woven fabrics with rather smaller quantities, especially from 1 to 5%by weight. The hand or handle of the treated material will, of course,depend on the amount of polythiol employed and by simple experiment theleast amount of polythiol required to give the desired effect mayreadily be determined. Further, the construction of the fabric alsoinfluences the amount of polythiol required.

The desired effects are not fully obtainable unt1l the polythiol on thematerial has substantially cured. At ordinary temperatures this may takefrom five to ten days or even longer. The curing reaction can, however,be accelerated greatly by the use of a catalyst, and generally 1t 18preferred to add the catalyst to the material to be treated at the sametime as the polythiol is applied although it may be added before orafterwards if desired. The curing time can be controlled by selecting anappropriate catalyst and the choice of ccuring time will depend on theparticular application of the process according to the invention. Thecatalysts may be organic or inorganic bases, siccatives, oxidativecuring agents, and free-radical catalysts such asazodi-isobutyronitrile, peroxides and hydroperoxides, or combinations ofthese. As organic bases there may be used pnmary or secondary amines,especially the lower alkanolamrnes, e.g. monoand di-ethanolamine, andlower polyammes, e.g. ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propane-1,2- dramme,propane-1,3-diamine, and hexamethylenediamine. As inorganic bases theremay be used the water-soluble oxides and hydroxides, e.g. sodiumhydroxide, and also ammonia. Examples of suitable siccatives arecalcium, copper, iron, lead, cerium, and cobalt naphthenates. Examplesof peroxides and hydroperoxides which may be used are cumenehydroperoxide, tert.-butyl hydroperoxide, dicumyl peroxide, dioctanoylperoxide, dilauryl peroxide, methyl ethyl ketone peroxide, di-isopropylperoxydicarbonate, and chlorobenzoyl peroxide. Other types of catalystsinclude sulphur, and sulphur-containing organic compounds in which thesulphur is not exclusively present in mercaptan groups, namely,mercaptobenzothiazoles or derlvatives thereof, dithiocarbamates, thiuramsulphides, thioureas, disulphides, alkyl xanthogen disulphides, or alkylxanthates.

The fibres and fabrics are preferably treated at a pH greater than 7,typically 7.5 to 12: under acid conditions the polythiols tend to curemore slowly.

The amount of catalyst used can vary widely. However, in general from0.1 to 20%, preferably 1 to 10%, by weight based on the weight ofpolythiol used is required, although much larger quantities can be used.

Curing of the polythiol is also assisted by using elevated temperaturesand it especially fast results are required then temperatures in therange of 30 to C. may be used. High humidities also tend to acceleratecuring in the presence of catalysts. The polythiol, and the catalyst ifdesired, can be applied to the keratinous material in conventional ways.For example, where wool tops or where fabric is to be treated,impregnation by padding or by immersing the material in a bath may beused. If garments or garment pieces are to be treated than it isconvenient to spray them with the polythiol, and more convenient stillto tumble the garments in a solution of the polythiol. For the lattermethod a dry-cleaning machine is a particularly useful apparatus forcarrying out the process.

If a shrink-resist treatment is required, then it is usually moreconvenient to apply the polythiol to the fabric although, as previouslystated, it may be applied to the fibres in the form of, e.g. tops orsliver. The fabric may be flatset before or after treatment with thepolythiol and by this means the fabric will, in addition to retainingsubstantially its original dimensions, also retain its flat smoothappearance during wear and after washing. It should be stated, however,that fiat-setting may not be necessary or even desirable with certaintypes of cloth. Flat-setting is normally carried out either by treatingthe cloth with steam at superatmospheric pressure, or by treating thecloth with steam at atmospheric pressure in the presence of a settingagent and moisture and maintaining the cloth in a flat state.Flat-setting may also be achieved by applying high concentrations of areducing agent and a swelling agent, and maintaining the cloth in a fiatstate during washing off the excess reagents. In another methodflatsetting may be achieved by impreg a the material with a swellingagent and an alkanolamine carbonate, e.g. urea and diethanolaminecarbonate, drying the mate and then semi-decatising it. Of course, ifdesired, the fabric may be set in the presence of the polythio thuseffecting setting and shrinkproofing treatments simultaneously.

If a durable press treatment is required, there are a number of waysthis may be achieved. One method is to treat the material with thepolythiol, make the material up into garments or garment pieces andinsert therein pleats or creases, using reducing agents, bases, orsuperheated steam as setting agents. Again, the polythiol may be appliedto the fibres at any stage during the manufacture of the fabric, e.g. intop form, in yarn, or in fabric form. If desired, agents which block thethiol groups of the wool, e.g. formaldehyde or higher aldehydes, may beapplied to the creased or pleated garments after curing the polythiol.

A preferred method of applying the polythiol to obtain a durable presseffect comprises treating the made-up garment or garment piece, whichalready has the desired creases or pleats imparted thereto, with thepolythiol dissolved in an organic solvent. In this method it isessential that the polythiol is applied in an organic solvent becausetreatment with aqueous systems would only serve to remove the creases orpleats already set in the fabric.

Another method, which is primarily concerned with the production ofdurable press pleats or creases only, comprises impregnating the fabricin the area where a crease or pleat is to be inserted with thepolythiol, imparting the crease or pleat, and maintaining it in thisposition whilst heat and pressure are applied.

A further method, for flat-setting and shrinkproofing keratinousfabrics, comprises treating the fabric with a setting agent and settingit in a flat configuration by heating the fabric while wet, impregnatingit with an aqueous emulsion or dispersion of the polythiol and catalyst,drying and heating the fabric, and curing the polythiol. Finally thefabric is made into garments, and creases or pleats set therein ifdesired by steaming in the presence of a setting agent such asmonoethanolamine sesquisulphite.

The setting of the fabric, whether carried out before or after treatmentwith the polythiol, may be effective using any of the known methods, forexample by means of setting agents, e.g. reducing agents, bases, water,and superheated steam. Monoethanolamine sesquisulphite is the mostfrequently used setting agent and may be used in association with aswelling agent, e.g. urea.

The compositions used in the process of this invention may containantisoiling, antistatic, bacteriostatic, rotproofing, flameproofing andwetting agents. They may also contain water-repellents such as paraifinwax, and fluorescent brightening agents.

The invention will now be illustrated by reference to the followingexamples. Unless otherwise specified, parts and percentages are byweight.

The treated samples of cloth were washed at 40 C. for one hour in anEnglish Electric Reversomatic washing machine in an aqueous solutioncontaining, per litre, 2 g. of soap flakes and 0.8 g. of anhydroussodium carbonate, using a liquor/sample ratio of about 30:1. The sampleswere removed, rinsed in cold water, spun in the machine, and then driedfor 30 minutes in a Parnall Tumble Drier on full heat. Shrinkage wasmeasured as the difference in dimensions of the fabric before and afterwashing. .Area shrinkage was calculated from linear shrinkagemeasurements. I

The polythiols employed were prepared as follows:

A mixture of glycerol (184 g.), thioglycollic acid (552 g.),toluene-p-sulphonic acid (4 g.), and perchloroethylene (500 ml.) washeated under reflux in an atmosphere of nitrogen in such a manner as toentrain water formed during reaction. After 5 hours, 104 ml. water wascollected (calculated quantity 108 ml.); the product partially separatedfrom the perchloroethylene on cooling. The solvent was removed and theproduct was washed with water and dried to yield 600 g. of substantiallypure glycerol tris (thioglycollate), a clear liquid having a thiolcontent of 8.88 equiv./kg. (theory, 8.93 equiv./kg.).

In a similar manner the following materials were prepared: 1,1,1trimethylolpropane tris(thioglycollate) (thiol content 7.45 equiv./kg.,theory 8.43), 1,1,1-trimethy olethane tris( h og ycol ate) V hiol.content 8.30

equiv./kg., theory 8.78), hexane-1,2,6-triol tris(thioglycollate) thiolcontent 7.72 equiv./kg., theory 8.40), dipentaerythritoltetrakis(thioglycollate) (thiol content 7.30 equiv./kg., theory 7.27),glycerol tris(Z-mercaptopropionate) (thiol content 7.5 8 equiv./kg.,theory 8.43), and the thioglycollate of a styrene-allyl alcoholcopolymer. The styrene-allyl alcohol copolymer had an average molecularweight of 1600 and contained 5.35 hydroxyl groups per average molecule.The ester had a thiol content of 2.15 equiv./kg., i.e. about of thecalculated value for a pentakis(thioglycollate). Pentaerythritoltetrakis(thioglycollate) and tetrakis(3-mercaptopropionate), anddipentaerythritol hexakis(thioglycollate) andhexalcis(3-mercaptopropionate) are available commercially.

A mixture of Empol 1043 g.), Z-mercaptoethanol (26 ml., 29.5 g.),toluene-p-sulphonic acid (1 g.) and perchloroethylene ml.) was heated toreflux for 16 hours under nitrogen in such a manner as to remove waterformed during the reaction (7.6 ml.). The solution was washed withwater, and stripped to yield 111 g. of a pale yellow oily liquid havinga thiol content of 2.20 equiv./kg., (theory approximately 2.8equiv./kg.).

In place of perchloroethylene, other solvents may be used, e.g. toluene.

Empol 1043" denotes a trimerised unsaturated C fatty acid, having amolecular weight of about 800 and a carboxyl content of 3.42 equiv./kg.it was obtained from Unilever-Emery N.V., Gouda, Holland.

In one example, a polythiol of this invention is applied as an aqueousemulsion. Emulsions containing the polythiol dispersed in an aqueousphase, an emulsifying agent (such as an adduct of a long-chain primaryaliphatic amine and ethylene oxide), and, optionally, a protectivecolloid (such as sodium carboxymethylcellulose or the sodium salt of amethyl vinyl ether-maleic anhydride copolymer) are particularlyconvenient for carrying out the treatment of keratinous material.

EXAMPLE I The cloth used was a wool flannel of approximately g. persquare metre; the pH of its aqueous extract was 3J1. The flannel waspadded with a 3% solution of the polythiol in trichloroethylene,containing 10% of monoethanolamine based on the weight of the polythiol,such that the uptake of the polythiol was 8% and that ofmonoethanolamine was correspondingly 0.8%. The solution also contained5% of ethanol to complete solution of the monoethanolamine. Then theflannel was dried at 50 C. in a fanned oven, and stored at roomtemperature with free access to air. The samples were Washed and theirshrinkage was measured. A sample of flannel was also subjected to thissevere washing but without prior treatment with a polythiol. Table Ishows the results obtained.

EXAMPLE II The test described in Example I was repeated, using otherpolythiols. The wool flannel used was similar to that in Example I, butthe pH o its aqueous extract was 7.0.

TABLE II Area shrinkage (percent) after- 1 2 8 day days day Untreated22. 5 22. 2 22. 2 Treated with:

Pentaerythrltol tetrakis(thioglycollate) 7. 7 9. 3 Dipentaerythritoltetrakis(thioglycollate) 14. 5 8. 7 Dipentaerythritol hexakis(thioglycollat l0. 5 7 3 Dipentaerythrltol hexakis (3-mercaptopropionate 13. 1 Castor oil tris (thiolglycollate). 11. 3 7. 4Styreneallyl alcohol poly-(thioglycollate) 15. 12. 7 Glycerol tris(thioglycollate) 10. 0 10. 7 Glycerol tris (thioglycollate) 1 a 15. 0Glycerol tris (2-mercaptoproplonate) 1 10. 7 Glyceroltris(thioglycollate) l 4 17.3 16. 8 14. 6 Pentaerythritol tetrakis(thioglycollat 14. 5 12. 6 Pentaerythritol tetrakis (thioglycollate)15.9 14. 5 9.4 Pentaerythrltol tetrakis (thioglycollate) 16. 8 7. 91,1,1-t1imethylolpropane tris(thioglycollat 19. 2 6. 41,1,1-trlmethylolpropane tris(thiog1ycollate) 18. 6 18. 6 5. 0 Mannitolhexakis (thioglycollate) 1 2 16. 5

1 Uptake of the polythiol was 3%. B Uptake of monoethanolaniine was0.3%. 8 Catalyst was 1.2% of calcium nephthenate (containing 5% Ca). 4Catalyst was 0. 3% of tetramethylthiuram disulphide. 5 Catalyst was0.16% of diethylenetriarnine.

Catalyst was 0.8% of di-isopro yl xanthogen disulphide. Catalyst was0.8% of tetrabuty thiuram disulphide.

EXAMPLE III This example illustrates the use of a polymercaptan of thisinvention with another kind of polymercaptan or with an epoxide resin.The procedure described in Example 11 was followed, and the results aregiven in Table III.

Thiol A denotes the bis(thioglyco1late) of a polyoxypropylene glycolhaving an average molecular weight of by the standard procedure.Untreated slubbing, on washing after 2 days and 8 days, shrunk linearlyby 28.0 and 28.3%, whereas the results for treated slubbing were 15.0and 11.5%.

EXAMPLE V An aqueous emulsion containing pentaerythritol tetrakis(thioglycollate) was prepared as follows.

Sodium carboxymethylcellulose (1 g.) was dissolved in water at 70-80 C.,and to the solution, which had been allowed to cool, were added 100 g.of the polythiol and 10 g. of an anionic emulsifying agent (an adduct of1 mol. of a mixture of n-alkyl primary amines containing 16 to 18 carbonatoms in the molecule with 70 mol. of ethylene oxide), and the whole wasstirred with a highspeed stirrer for 5 minutes.

A 12 g. portion of this emulsion was diluted with 276 g. of water, andwith 12 g. of a 1% aqueous solution of diethylenetriarnine as catalyst,and padded onto wool fiannel as described in Example II; the thiol wasthen allowed to cure. The uptake of the thiol was 2%, while that ofdiethylenetriarnine was 0.04% The wool flannel, on being washed afterone days curing at room temperature, shrunk by only 9.8%

In a second experiment, an emulsion was prepared as described above butsubstituting for the tetrathiol an equal weight of Thiol B.

Four grams of the emulsion of Thiol B were mixed with 12 g. of theemulsion of pentaerylthritol tetrakis(thioglycollate), '12 g. of 1%aqueous diethylenetriarnine solution, and 272 g. water, and the mixturewas padded on to wool as described earlier in this example. Then thecloth was cured for 1 day at room temperature and washed, when theshrinkage in area was only 8.3%.

We claim:

1. A process for modifying keratinous fibrous material, which comprises(1) treating the material with a polythiol ester of the formula Thiol Bdenotes Hycar MTBN of B. F. Goodrich Chemical Co. According to themanufactures, it has a number average molecular weight of about 1700,and is a R (C0) (0R1) O CQLRLSH] thiol-terminated polymer containingabout 21 butadiene L /v 11 units and 7 acrylonitrile units per averagemolecule. It F COOH comprises structures which may be represented by theL or f mula wherein HS F/CHgCEbCHCH) l SH R represents a hydrocarbonradical, contaimng a /a k l chain of at least 3 and at most carbonatoms,

N 50 and selected from the group consisting of ali- Epoxy resin Adenotes a polyglycidyl ether of 2,2- phatic radicals,bis(4-hydroxypheny1)propane having a 1,2-epoxide con- R represents analkylene group containing at least tent of 5-5.2 equiv./kg. 2 and atmost 6 carbon atoms,

TABLE III Area shrinkage (percent) after- Per- Per- Per- Ester cent(Jo-reactant cent Catalyst cent lday 2days 8daysGlyceroltris(thioglycollate) 6 Ethylene glycolbis(thioglycollate). 2Monoethanolamine 0.8 14.0 11.2 8.8 Do s Thio .-do 0.8 12.6 10.8Pentaerythrltoltetrakis(thio- 6 Ethylene glycol bis(3-mercaptopro- 2Diethylenetriamine... 0.16 13.1 12.2

gtlycollate pionate).

Do 2 ThiolB 1 N 14.0 10.3 2 .....dr 1 do 9.3 9.3 6.9 1.5 Epoxy resinA1.5 Diethyleuetriamine-.. 0.06 9.8 9.8

l The treated samples were cured by heating for 5 minutes at 150 C.before storing.

EXAMPLE IV Wool slubbing was padded to 300% uptake with a solution inperchloroethylene of 1,1,1-trimethylolpropane tris (thioglycollate) andmonoethanolamine such that the pick-up of the polythiol was 8% and thatof monoethanolamine was 0.8%. The slubbing was dried at C. for 30minutes, and allowed to stand in contact with air. The elfectiveness ofthe treatment was assessed by measuring the shrinkage of samples of theslubbing that took place when the samples were washed (enclosed incotton bags) 2. Process according to claim 1, wherein the polythio esteris of the formula in which R represents an alkylene hydrocarbon group offormula C H where m is an integer of at least 1 and at most 12, and R,p, and q have the meaning assigned in claim 1.

3. Process according to claim 2, wherein R represents a radical selectedfrom the group comprising those of the formulae 4. Process according toclaim 1, wherein the polythiol ester is of the formula R EOCO-R -SH],,in which R denotes an aliphatic hydrocarbon radical having at least 3and at most 6 carbon atoms, R represents an alkylene hydrocarbon groupcontaining 1 to 12 carbon atoms, p has the meaning assigned in claim 1.

5. Process according to claim 1, wherein the polythio ester is of theformula co-o-av-sn Escort] in which R and p each have the meaningassigned in claim 1,

R represents an alkylene group of formula C H where n is an integer ofat least 2 and at most 12, and

u is selected from the class consisting of zero and 1.

6. Process according to claim 5, wherein R denotes a group selected fromthose of the formulae CH CH and CH CH(CH 7. Process according to claim12, wherein the polythiol ester is of the formula R ECO0-R SH] in whichR* represents an alkylene group of formula C H where n is an integer ofat least 2 and at most 12, and R and p each have the meaning assigned inclaim 1.

8. Process according to claim 7, where R denotes a group selected fromthose of the formulae CH CH and --CH CH(CH 9. Process according to claim1, wherein 0.5 to 15% by weight of the polythiol ester is used, based onthe weight of keratinous material treated.

10. Process according to claim 1, in which a catalyst for curing thepolythiol is also applied, said catalyst being chosen from the groupcomprising bases, siccatives, oxidative curing agents, free-radicalcatalysts, sulphur, mercaptobenzothiazoles, dithiocarbamates, thiuramsulphides, thioureas, organic disulphides, alkyl xanthogen disulphides,and alkyl xanthates.

'11. Process according to calim 1, in which keratinous fibres aretreated with the polythiol at a pH of from 7.5 to 12. a

12. Process according to claim 1, wherein the treated keratinousmaterial is heated to a temperature in the range 30 to 80 C- to cure thepolythiol.

13. Process for subjecting keratinous fibrous material to ashrink-resist treatment which comprises applying to the material apolythiol ester of formula in which R, R R a, x, y and p have thesignificance indicated in claim 1, (2) making up the material into atleast a portion of a garment, and (3) setting the fabric in the desiredconfiguration.

16. Process for subjecting a keratinous fabric to a durable presstreatment which comprises applying a polythiol ester of the formula inwhich R, R R a, x, y and p have the significance indicated in claim 1,to the fabric already set in the desired configuration.

17. Process for flat-setting and shrinkpoofing a keratinous fabric,comprising treating it with a setting agent and setting it in a flatconfiguration by heating the fabric while wet, impregnating it with apolythiol ester of the in which R, R R a, x, y and p have thesignificance indicated in claim 1, drying and heating the fabric, andcuring polythiol.

118. Fibrous keratinous material bearing thereon a. polythiol ester ofthe formula V 03 ).011 L w in which R, R R a, x, y and p have thesignificance indicated in claim 1, in the cured or still curable state.

19. Process for modifying keratinous fibrous material which comprises 13(1) treating the material with a polythiol ester of most 2, with theproviso that x and y are unthe formula equal,

q is an integer of at least 1 and at most 4, with the proviso that (p+q)is at most 7, and 5 (2) curing the polythiol ester on the material.

(ql)(:v'-l) [R [00011] References Cited F UNITED STATES PATENTS3,437,519 4/1969 -Friedl 117-141 10 3,223,413 12/1965 Bergen s 12s3,477,804 11/1969 Fricdl 8-128 wherein R denotes a hydrocarbon radicalhaving a chain DONALD LEVY Primary Examiner of at least 3 and at most 60carbon atoms and selected from the group comprising aliphatic 15 CANNONAssistant Exammer and araliphatic radicals,

R denotes a divalent radical of formula C H where m' is an integer of atleast 1 and at most 8--115.5, 115.6, 115.7, 11-6, 116.2, 116.3, 127.6,128 A, 12, DIG 4, DIG 11, DIG 21; 2-243; 38-144; 117-138.8

p denotes an integer of at least 3 and at most 6, 20 F, 138.8 N, 138.8UA, 139.4, 141, 143 A, 145, 161 LN, x and y each denote an integer of atleast 11 and at 161 UZ, 161 UN, 161 ZB UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 3,706,5 7 Dated December 9 197Inventor(s) BRYAN DOBINSON ET AL 7 It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 10, line 51, after "phatic" insert and araliphatic C I Column 11,line &4, after "formula" delete "C H and insert C H v I Signed andsealed this mm day or June 1971;.

(SEAL) Attest:

EDWARD mmmmcusmm. c. MARSHALL 1mm Comigsi oner of Patents Atte stingOfficer

